CN102189897B - Tire having tread with an internal softer transition rubber layer containing short fiber reinforcement - Google Patents
Tire having tread with an internal softer transition rubber layer containing short fiber reinforcement Download PDFInfo
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- CN102189897B CN102189897B CN201110063034.1A CN201110063034A CN102189897B CN 102189897 B CN102189897 B CN 102189897B CN 201110063034 A CN201110063034 A CN 201110063034A CN 102189897 B CN102189897 B CN 102189897B
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- rubber
- rubber layer
- tire
- tread
- transition
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 197
- 239000005060 rubber Substances 0.000 title claims abstract description 197
- 230000007704 transition Effects 0.000 title claims abstract description 37
- 239000000835 fiber Substances 0.000 title claims abstract description 27
- 230000002787 reinforcement Effects 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 76
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- 230000002600 fibrillogenic effect Effects 0.000 claims description 22
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
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- LLMLGZUZTFMXSA-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzenethiol Chemical compound SC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl LLMLGZUZTFMXSA-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
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- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
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- 150000002357 guanidines Chemical class 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LUPNKHXLFSSUGS-UHFFFAOYSA-M sodium;2,2-dichloroacetate Chemical compound [Na+].[O-]C(=O)C(Cl)Cl LUPNKHXLFSSUGS-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical class N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
- B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
- Y10T152/10513—Tire reinforcement material characterized by short length fibers or the like
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a tire having tread with an internal softer transition rubber layer containing short fiber reinforcement. The invention relates to a tire having a rubber tread comprised of a circumferential outer cap rubber layer which contains a tread running surface and an underlying undertread layer of softer rubber than said outer tread cap rubber layer wherein said undertread layer rubber composition contains short fiber reinforcement.
Description
Technical field
The present invention relates to the tire of sandwich configuration rubber tread, comprise containing softer inside transition rubber layer of week in circumferential crown of tyre (the outer tread cap) rubber layer of tyre surface running surface, vertical direction, the latter is as tread cushioning layer (undertread) rubber layer, be positioned between the circumferential tread-rubber of described crown of tyre rubber layer and underlay (underlying) basic unit, the rubber composition of wherein said softer interior transition rubber layer is containing fibrillation aramid fiber short fibre intensifier (short fibrillated aramid fiber reinforcement).
Background technology
The tyre surface of aerated rubber tyre generally disposes circumferential crown of tyre rubber layer and the underlay tread-rubber basic unit (under described crown of tyre rubber layer) of the running surface contacting with ground containing tire.
Cover tire canopy be generally for impel tire running surface there is suitable tyre surface resistance to abrasion, to good dry/wet tack of road with promote tire to handle and the suitable rigidity of driving.
The challenge facing is: impel more soft vehicle ride to be different from the mode of practice in the past, then in the meaning of more soft vehicle ride, improve the traveling comfort of vehicle.
A kind of method of impelling more soft vehicle ride is to adopt the rubber composition of softer (rigidity appropriateness reduces) to make tyre surface.
Can make tread rubber composition stiffness degradation or make it more soft method has: for example, and with the more granulated rubber reinforcer of low surface area; In rubber composition with reinforcer content still less and/or in rubber composition with more rubber processing oil content.
But, expect that the tread rubber composition of this class stiffness degradation (softer) has more undesirable tread properties, as wet/arterial highway road tack is lower, and poor resistance to abrasion, this will cause the increase of tread wear.In addition, also expect that the manipulation of vehicle and/or driving performance are also subject to negative effect.
For the present invention, propose to adopt than the middle transition rubber layer of the rubber of crown of tyre rubber softer (rigidity suitably reduces) under described crown rubber layer and between crown rubber layer and tread-rubber basic unit.
From improving the viewpoint of vehicle riding comfort and tyre surface road-holding property, choosing a little of facing is: this more soft transition rubber layer (much softer than crown rubber) that much soft rubber composition (Xiao A hardness the is very low) formation that has significantly high low strain modulus performance on the athwartship plane by the circumferential surface at tyre surface and tyre surface is provided.
By this way,, when improving the more soft vehicle ride of tire itself, still keep wet/dry tack and the tyre surface resistance to abrasion of crown of tyre rubber expectation.
But, can predict, use softer intermediate rubber layer to estimate the rigidity that makes tyre surface on its athwartship plane (side-side surface direction) to reduce, thereby sacrifice manipulation and driving (turning to) performance of tire.
For object of the present invention, will to middle transition rubber layer compared with soft rubber composite in comprise into the dispersion of fibrillation aramid fiber short fibre intensifier, with tread rubber layer in the middle of promoting in its circumferentially and horizontal rigidity in (side-side surface direction), thereby promote manipulation and the driving performance of tire to evaluate.
Fortunately, for intermediate rubber layer, the orientation of fibrillation aramid fiber short fibre in the circumferential surface of tyre surface running surface can realize with calendering or the extrusion molding of traditional rubber composition, thereby promotes the humidification of rubber composition layer in the circumferential surface of tyre surface interlayer.
But, an importance of the present invention is to evaluate this fiber orientation of fibrillation aramid fiber short fibre, whether also can provide the humidification on tyre surface interlayer laterally circumferential (side-side surface direction) to the rubber composition layer of the middle soft rubber layer of tyre surface.
In specification sheets of the present invention, term " rubber " and " elastic body ", all use that makes, are used, unless otherwise prescribed interchangeably.Term " rubber composition ", " compounded rubber " and " rubber composite ", all use that makes, be used to refer to interchangeably " with various ingredients blend or the rubber that mixes ", and term " compound " are relevant to " rubber composition ", unless otherwise noted.This class term is that the technical personnel in rubber mix and rubber combined technical field is known.
In specification sheets of the present invention, term " phr " refers to that each material is with respect to every 100 parts by weight of rubber or elastomeric umber.Term " solidifies " and " sulfuration " used interchangeably, unless otherwise noted.
Summary of the invention
According to the present invention, provide the tire with the tyre surface that comprises circumferential crown of tyre rubber layer and the transition rubber layer below described crown of tyre rubber layer (tread cushioning layer rubber layer);
Wherein said crown of tyre rubber layer comprises pattern block and groove configuration, and the pattern block of projection has the tyre surface running surface (described running surface is intended to contact with ground) on described pattern block outside face, groove between described pattern block,
Wherein said transition rubber layer is excluded outside tire running surface, and is non-porous (non-cellular) rubber composition;
The rubber composition of wherein said transition rubber layer comprises:
(A) conjugated diene based elastomeric, as natural (cis 1,4-polyisoprene) blend of rubber, cis Isosorbide-5-Nitrae-poly-butadiene rubber and styrene/butadiene copolymers rubber (styrene/butadiene copolymers rubber prepared by organic solution or aqueous emulsion polymerization);
(B) 0～at the most approximately 30 phr or approximately 5～approximately 25 phr reinforcers, comprise
(1) rubber reinforcement carbon black, or
(2) amorphous synthetic silica (precipitated silica), or
(3) combination of rubber reinforcement carbon black and precipitated silica;
The stiffness properties of wherein said transition rubber layer (tread cushioning layer rubber layer) is as follows:
(C) Xiao A hardness (23 ℃) is 20～approximately 50, or approximately 25～approximately 45, and preferably than low at least 10 Xiao A hardness of the Xiao A hardness of the rubber composition of crown rubber layer (23 ℃) unit;
(D) 100% parallel (circumferentially) tensile modulus is at least 1 MPa, and
(E) 100% vertical (laterally) tensile modulus is at least 0.7 MPa;
Wherein said underlay tyre surface (tread cushioning layer) rubber layer contains approximately 0.25～approximately 10 phr, preferably the dispersion of approximately 0.5～approximately 5 phr fibrillation aramid fiber short fibre slurry.
In fact, the Xiao A hardness of the rubber composition of crown rubber layer (23 ℃) can be, for example, and 55～approximately 75.
Shore hardness and the stress-strain modulus parameter complete list of the rubber composition of underlay (transition or tread cushioning layer) tread rubber layer are shown in lower Table A.
table A
comfort index Xiao A hardness (23 ℃)
20～50, or 25～45
manoeuverability index
The stress-strain modulus of interior transition rubber layer under 100% strain
Minimum parallel modulus
11 MPa
Minimum vertical modulus
10.7 MPa
1ASTM?D412。Parallel 100% strain (100% dynamic percentage elongation) modulus is measured from solidifying texture (grain) direction of extruded rubber sample.Vertical 100% strain (100% dynamic percentage elongation) modulus is measured in the direction of texture from solidifying extruded rubber samples vertical.
In one embodiment, described fibrillation aramid fiber short fibre slurry is upwards obviously orientated (being generally parallel to rubber texture) in underlay transition tread rubber layer week.
This orientation of fibrillation aramid fiber short fibre slurry be by, for example, rubber is extruded as uncured tread ply band shape is caused by high shear, and therefore along the texture orientation of extruding uncured rubber, uncured rubber be at high temperature cured subsequently (sulfuration).
Fortunately underlay transition tread rubber composition is not rubber foams composite, has therefore got rid of rubber foams configuration.
The aramid fiber material that fibrillation aramid fiber slurry is used can be described as, and for example, long-chain synthesis of aromatic polyamide, is all connected on 2 aromatic rings at least about 85% aramid key therein.For example, also can be seen as be mainly PPTA to aramid fiber.
Fibrillation aramid fiber also can be counted as, for example, have trunk portion and a lot of along its most of length the utmost point short aramid fiber from the diameter of the trunk extension fibril more much smaller than the trunk diameter of its extension.Relevant exemplary description, is shown in U.S. patent 4,871,004.Aramid fiber also can be contained in the slurry form in natural rubber matrix by aramid fiber, as, for example, the Kevlar of E.I.Du Pont Company
tMproduct provides.
An importance of the present invention is to provide has minimum parallel and horizontal (perpendicular to the direction of the parallel direction of rubber extruding texture) tensile modulus performance and Xiao A hardness value underlay transition tyre surface (tread cushioning layer) rubber composition in approximately 20～approximately 50 scopes under 100% dynamic strain.
For underlay tyre surface (tread cushioning layer) rubber composition, can be with multiple rubber reinforcement carbon black.The various typical rubber that can consider strengthen carbon blacks can be for example
the Vanderbilt Rubber Handbook(1978), the 417th page is found.
In practice, underlay transition tyre surface (tread cushioning layer) rubber composition can be with, for example, at least 1 condition of readiness (unproductive) blend step manufacture in inner rubber mixer, usually in succession series at least 1, common 2 discrete and condition of readiness blend steps alone or manufacture in the stage, therein, in inner rubber mixer or optionally, in mill, the silicon dioxide and/or carbon black and the chopped fiber that first mix diene based elastomer and regulation, then be final blend step (productivity blend step), will be within the time of lower temperature and much shorter in mill blend curing agent (sulphur and sulfur curable accelerator).
After each inner rubber blend step, require traditionally rubber composition (composite) in fact in internal rubber mixer mixer, take out and be cooled to below 40 ℃, perhaps be cooled to approximately 20 ℃～approximately 40 ℃, and then add-back inner rubber mixer, to carry out follow-up blend step or stage.
This unproductive mixing is followed productivity and is mixed, and is that in this field, technical personnel is known.
The shaping of tyre element is intended carrying out with traditional approach, for example, and by extruding or rolling the half finished rubber parts that rubber composition provides shaping, as tread ply.This forming process of tyre surface (layer) is that person skilled in art is known.
Should be understood that tire, as product, is for example, to make by the assembly set being shaped under high temperature (, 140 ℃～170 ℃) and high pressure in suitable mould and solidify its parts.This practice is that these those skilled in the art are known.
Relevant technologies those of skill in the art very easily understand: rubber composition will be undertaken compound by method known in rubber combined technical field, as mix multiple sulphur-vulcanizable component rubber and various typical additives material, as discussed before this paper, as, auxiliary curing agent is as sulphur, activator, retarding agent and accelerator; Processing additives, as RUBBER PROCESS OIL, the resin that comprises tackifying resin, silicon dioxide and plasticizer, filler, pigment, aliphatic acid, zinc oxide, wax, antioxidant and atiozonant, peptizer and reinforcing material, as carbon black.Just as is known to the person skilled in the art, depend on the intended purpose of sulphur-can vulcanize and sulfur vulcanization material (rubber), select above-mentioned additive and use habitual amount.
If with the aliphatic acid that can comprise stearic acid, its typical content is approximately 0.5～approximately 3 phr.The typical content of zinc oxide is approximately 1～approximately 5 phr.The typical content of wax is approximately 1～approximately 5 phr.Conventional ceresine wax.The typical content of peptizer is approximately 0.1～approximately 1 phr.Typically peptizer can be, for example, and pentachloro-thiophenol and dibenzamido Diphenyl disulfide.
Sulfuration is having sulfur vulcanization agent to carry out under existing.The example of applicable sulfur vulcanization agent comprises elemental sulfur (free sulphur) or to sulfur vulcanization agent, for example, and the polysulfide of curing amine, polymerization or sulphur olefin adducts.Preferably sulfur vulcanization agent is elemental sulfur.As known to persons skilled in the art, the consumption of sulfur vulcanization agent is approximately 0.5～approximately 4 phr, or in some cases, even high approximately 8 phr, preferably approximately 1.5～approximately 2.5 phr, sometimes approximately 2～approximately 2.5 phr.
Accelerator is used for controlling required time of cure and/or temperature and improves the performance of sulfide.In one embodiment, can use single accelerator system, i.e. primary accelerator.Traditionally and preferably, total consumption of primary accelerator is approximately 0.5～approximately 4 phr, preferably approximately 0.8～approximately 2.5 phr.In another embodiment, in order to activate and improve the performance of sulfide, can use the combination of primary accelerator and time accelerator, the consumption less (approximately 0.05～approximately 3 phr) of inferior accelerator.Can expect, the combination of these accelerators can produce synergy to final performance, better a little than the resulting performance of alone wherein arbitrary accelerator.In addition, can also be with not affected by general processing temperature but produce and be satisfied with curing delayed action accelerator under general curing temperature.Also can use vulcanization retarder.Can be used for suitable accelerator type of the present invention is amine, disulfides, guanidine class, Thiourea, thiazoles, thiurams, sulfinylamines, dithiocarbamate and xanthic acid salt.Preferably primary accelerator is sulfenamide.If with time accelerator, preferably guanidine, dithiocarbamate or thiuram compound of time accelerator.
The mixing of rubber composition can preferably be undertaken by aforementioned order mixing method.For example, can within least 2 stages, that is, at least one unproductive (condition of readiness) stage, then, in a productivity (finally) mix stages, mix each composition.Final curing agent generally mixes in the terminal stage that is referred to as traditionally productivity or final mix stages, mixes and generally under the lower temperature of the mixing temperature of the unproductive mix stages than previous or final temperature, carries out therein.Term " unproductive " and " productivity " mix stages are that the technical personnel in rubber mix field is known.
Accompanying drawing explanation
Accompanying drawing provides with the form of Fig. 1 and Fig. 2, to provide intuitively the data of the interior contained compound A～E of table 2.
Accompanying drawing also provides with the form of Fig. 3, to illustrate the cross section of tyre surface of the present invention.
Accompanying drawing also provides with the form of Figure 4 and 5, to illustrate to have on a small quantity, if had, and the tire fiber enhancer of the conventional tire fiber enhancer of fibrillation and a large amount of fibrillation.
accompanying drawing
Fig. 1 means the bar chart of the Xiao A hardness (23 ℃) of each compound (rubber composition) A～E.
As seen from Figure 1, representative is intended to the rubber composition of the crown of tyre rubber layer that contacts with ground, its Xiao A hardness value (23 ℃) is 66, far above 35,34 and 43 Shore hardness (23 ℃) value of being respectively of the rubber composite B, the C that propose for much soft underlay tread rubber composition and D.
From Fig. 1, also can see, the Xiao A hardness of rubber composition E (23 ℃) value 64 is very high and apparently higher than the Xiao A hardness value desired to underlay transition rubber layer (23 ℃) 20～50.
For comparing stress (tensile modulus) value, Fig. 2 has provided the relation of stress (MPa) that each compound (rubber composition) A～E represents with modulus and strain percentum, stress the lower strain area of 50～100% strain values on curve in particular, especially 100% strain value.
Fig. 3 is typical tyre surface section drawing, signal crown of tyre rubber layer (1), underlay transition tread rubber layer (2) and tread-rubber basic unit (3).
Fig. 3 illustrates the example in tyre surface of the present invention cross section, wherein
(A) Xiao A hardness of crown rubber layer composite (23 ℃) value is at least about 2.6 MPa for approximately 72,100% strain modulus level, and
(B) Xiao A hardness of underlay transition rubber composite (23 ℃) is that approximately 43 and 100% strain modulus level is approximately 2.7 MPa.
It is a small amount of or without the aramid fiber of a large amount of fibrillation in traditional fibers straight of fibrillation and Fig. 5 that Figure 4 and 5 are used for having in schematic diagram 4.
Especially, as seen from Figure 5, aramid fiber is fibrillation in a large number, with the fibril extending from the extensive entanglement of aramid fiber trunk.It is very important to implementing the present invention that this point is considered to, because (at final tyre surface transversely) provides humidification to curing rubber composite in the direction perpendicular to fiber orientation, described fiber is height-oriented in the grain direction of uncured rubber composite during uncured rubber composite profile extruded.
The specific embodiment
embodiment I
For evaluating the effect of adding the short aramid fiber slurry of fibrillation intensifier in the rubber composition as underlay transition tread rubber layer (tread cushioning layer rubber layer) in tyre surface, prepared rubber composition.
Rubber sample A representative for crown of tyre rubber layer compared with the silica-reinforced rubber composite of rigidity.
Rubber sample B representative is as the much soft rubber composition of underlay tread rubber layer candidate material.
Rubber sample C, D and E represent the rubber composition of the dispersion of rubber sample B and 3 phr fibrillation aramid fiber short fibre slurries and 0,20 or 30 phr carbon particulates filler intensifiers.
Rubber composition is by one or more inner rubber mixers, mixes each composition make with unproductive (NP) in succession and productivity (PR) blend step.
The basic components of rubber sample is shown in following table 1 and lists with weight portion, unless otherwise noted.
table I
unproductive blend step (NP), (being mixed into 160 ℃)umber
Natural rubber
10,55 and 60
Contained natural rubber 0 and 10 in aramid fiber slurry
Cis Isosorbide-5-Nitrae-poly-butadiene rubber
2variable
Fibrillation aramid fiber short fibre slurry
30 and 3
Carbon black (N550)
40 and 20
Precipitated silica
573 and 0
RUBBER PROCESS OIL is variable
Aliphatic acid
62
Zinc oxide 2
productivity blend step (PR), (being mixed into 110 ℃)
Sulphur and sulfur curable accelerator
72.6
1natural cis Isosorbide-5-Nitrae-polyisoprene rubber
2cis Isosorbide-5-Nitrae-poly-butadiene rubber Budene
tM1207, from Goodyear Tire & Rubber Company
3the fibrillation aramid fiber short fibre slurry masterbatch that comprises natural rubber and fibrillation short stock, Kevlar
tM/ NR (natural cis Isosorbide-5-Nitrae-polyisoprene rubber) masterbatch, containing the 23% Modified K evlar aramid fiber short fibre Merge from E.I.Du Pont Company
tMiF722.Aramid fiber short fibre slurry is with aramid fiber short fibre slurry itself, and its 0 or 3 phr, is reported in table 1
4rubber reinforcement carbon black N550, ASTM name
5precipitated silica Zeosil 1165 MP
tM, from Rhodia company
6aliphatic acid, mainly comprises stearic acid and a small amount of other aliphatic acid that mainly comprises palmitic acid and oleic acid
7sulphur and sulfenamide and thiurams sulfur curable accelerator.
Following table 2 has provided curing action and the multiple physical property of the rubber composition based on the interior basic components of table 1, and material content is with the weight portion with respect to every 100 parts by weight of rubber (phr) report.
table 2
1?ASTM?D412。Parallel 100% strain (100% dynamic percentage elongation) modulus records in the grain direction of curing extruded rubber sample in the sixth of the twelve Earthly Branches.Vertical 100% strain (100% dynamic percentage elongation) modulus is solidified extruded rubber samples vertical in the sixth of the twelve Earthly Branches and is recorded in the direction of texture.
From comfort index aspect by table 2, Xiao A hardness value 35,34 and 43 in the criterion scope 20～50 of only having rubber composition B, C and D to have respectively to drop on shown in Table A and shown in Fig. 1, these values are also far below the value 72 of rubber composition A, therefore much soft.
But the Xiao A hardness value 64 of rubber composition E is obviously greater than the much soft Xiao A hardness criterion scope 20～50 shown in Table A and therefore drops on outside this scope.
Think that this point is very important herein, because its explanation, reinforcer, i.e. the content of rubber reinforcement carbon black, when containing 3 phr fibrillation aramid fiber short fibre, should be lower than 30 phr.
From manoeuverability index aspect, by table 2, also can be seen and be shown in Fig. 2, only rubber composition C, D have satisfied parallel 100% strain that is greater than 1.0 MPa (100% dynamic percentage elongation) modulus value and vertical 100% strain modulus level that is greater than 0.7 MPa with E.
But, being easy to see, rubber composition E is also unsatisfactory, because its high Xiao A hardness value 64, the maxim 50 requiring than the comfort index of reporting in Table A is much bigger.
Therefore, obtain conclusion: only rubber composition C and D are satisfactorily for tread cushioning layer of the present invention (interior transition tread rubber layer), because they had both passed through the Xiao A hardness comfort index limit of stipulating in Table A, passed through again the manoeuverability index of stipulating in Table A, the parallel drawing modulus value under 100% dynamic strain is greater than 1 MPa and cross directional stretch modulus value is greater than 0.7 MPa.
Although for explanation object of the present invention has provided some typical embodiment and details, it will be obvious to those skilled in the art that and can do therein various changes and modification under the prerequisite that does not depart from the scope of the invention.
Claims (7)
1. the tire with rubber tread, described tyre surface is comprised of circumferential crown of tyre rubber layer, transition tread rubber layer and tread-rubber basic unit, and wherein transition tread rubber layer is between crown of tyre rubber layer and tread-rubber basic unit;
Wherein said crown of tyre rubber layer comprises pattern block and groove configuration, and the pattern block of projection has tyre surface running surface on described pattern block outside face, and groove is between described pattern block, and described transition rubber layer is ostracised outside tire running surface,
It is characterized in that described transition rubber layer is non-rubber foams composite;
The rubber composition of wherein said transition rubber layer comprises:
(A) blend of natural rubber, cis Isosorbide-5-Nitrae-poly-butadiene rubber and styrene/butadiene copolymers rubber;
(B) 0～at the most 30 phr reinforcer, comprises:
(1) rubber reinforcement carbon black, or
(2) precipitated silica, or
(3) combination of rubber reinforcement carbon black and precipitated silica;
The stiffness properties of wherein said transition rubber layer is as follows:
(C) Xiao A hardness (23 ℃) is 20～50, than low at least 10 Xiao A hardness of the Xiao A hardness of the rubber composition of crown rubber layer (23 ℃) unit;
(D) 100% parallel drawing modulus is at least 1 MPa, and
(E) 100% stretched vertically modulus is at least 0.7 MPa;
Wherein said transition rubber layer is containing the dispersion of 0.25～10 phr fibrillation aramid fiber short fibre slurry; With
The Xiao A hardness of the rubber composition of wherein said crown rubber layer (23 ℃) is 55～75.
2. tire as claimed in claim 1, is characterized in that, the rubber composition of described transition rubber layer is not containing rubber reinforcement carbon black or precipitated silica reinforcer.
3. tire as claimed in claim 1, is characterized in that, described transition rubber layer has following stiffness properties:
(A) Xiao A hardness (23 ℃) is 25～45, than low at least 10 Xiao A hardness of the Xiao A hardness of the rubber composition of crown rubber layer (23 ℃) unit,
Wherein said transition rubber layer is containing the dispersion of 0.5～5 phr fibrillation aramid fiber short fibre slurry.
4. tire as claimed in claim 3, is characterized in that, the rubber composition of described transition rubber layer is not containing rubber reinforcement carbon black or precipitated silica reinforcer.
5. tire as claimed in claim 3, is characterized in that, the rubber composition of described transition rubber layer contains 5～25 phr rubber reinforcement carbon blacks, but containing precipitated silica reinforcer.
6. tire as claimed in claim 3, is characterized in that, the rubber composition of described transition rubber layer contains 5～25 phr precipitated silica reinforcers, but containing rubber reinforcement carbon black.
7. tire as claimed in claim 3, is characterized in that, the rubber composition of described transition rubber layer is containing the combination of 5～25 phr rubber reinforcement carbon blacks and precipitated silica reinforcer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/724,440 US8439095B2 (en) | 2010-03-16 | 2010-03-16 | Tire having tread with an internal softer transition rubber layer containing short fiber reinforcement |
| US12/724,440 | 2010-03-16 | ||
| US12/724440 | 2010-03-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102189897A CN102189897A (en) | 2011-09-21 |
| CN102189897B true CN102189897B (en) | 2014-03-26 |
Family
ID=44276032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110063034.1A Expired - Fee Related CN102189897B (en) | 2010-03-16 | 2011-03-16 | Tire having tread with an internal softer transition rubber layer containing short fiber reinforcement |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US8439095B2 (en) |
| EP (1) | EP2366559B1 (en) |
| CN (1) | CN102189897B (en) |
| BR (1) | BRPI1101074A2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8701727B2 (en) | 2011-08-31 | 2014-04-22 | The Goodyear Tire & Rubber Company | Truck drive tire |
| AP2015008241A0 (en) | 2012-08-02 | 2015-01-31 | Amril Ag | Natural rubber containing nanocarbon |
| CN103131061B (en) * | 2013-03-05 | 2015-05-27 | 无锡宝通带业股份有限公司 | Energy-saving conveyer belt primer and preparation method thereof |
| WO2016104815A1 (en) | 2014-12-26 | 2016-06-30 | Compagnie Generale Des Etablissements Michelin | A tire having a tread comprising rubber composition comprising short fibers |
| FR3045630B1 (en) * | 2015-12-22 | 2018-01-19 | Compagnie Generale Des Etablissements Michelin | PULP COMPOSITE MATERIALS FOR MECHANICAL COUPLING |
| US10961372B2 (en) * | 2019-01-31 | 2021-03-30 | The Goodyear Tire & Rubber Company | Rubber composition containing dual polybutadiene elastomers with balanced filler reinforcement network, preparation and tire with component |
| EP3778264B1 (en) | 2019-08-15 | 2023-09-13 | The Goodyear Tire & Rubber Company | A tire tread and a tire comprising a tread |
| EP3778263B1 (en) | 2019-08-15 | 2022-06-22 | The Goodyear Tire & Rubber Company | A tire tread and a tire comprising a tread |
| EP3778262B1 (en) | 2019-08-15 | 2022-09-28 | The Goodyear Tire & Rubber Company | A tire tread and a tire comprising a tread |
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| US4739811A (en) * | 1982-10-20 | 1988-04-26 | Semperit Reifen Aktiengesellschaft | Pneumatic vehicle tire with radial ply carcass and tread member composed of a base layer situated closer to the tire axis and a cap layer arranged on top thereof |
| JP2668358B2 (en) * | 1987-04-22 | 1997-10-27 | 横浜ゴム株式会社 | Radial tire |
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| JPS59153606A (en) * | 1983-02-18 | 1984-09-01 | Mitsuboshi Belting Ltd | Puncture resistance tire |
| JPS60116505A (en) * | 1983-11-30 | 1985-06-24 | Sumitomo Rubber Ind Ltd | Bias tire |
| US4871004A (en) | 1988-02-17 | 1989-10-03 | The Goodyear Tire & Rubber Company | Rubber containing aramid pulp reinforcement |
| JP2862563B2 (en) * | 1989-06-05 | 1999-03-03 | 東洋ゴム工業株式会社 | Cap-based tires |
| US5576104A (en) * | 1994-07-01 | 1996-11-19 | The Goodyear Tire & Rubber Company | Elastomers containing partially oriented reinforcing fibers, tires made using said elastomers, and a method therefor |
| JPH11278015A (en) * | 1998-03-26 | 1999-10-12 | Sumitomo Rubber Ind Ltd | Studless tire |
| US20010006086A1 (en) * | 1998-11-02 | 2001-07-05 | The Goodyear Tire & Rubber Company | Pneumatic tire having specified bead structure |
| US6255379B1 (en) | 1999-09-16 | 2001-07-03 | The Goodyear Tire & Rubber Company | Rubber containing short fiber reinforcement with anchoring agent and articles, including tires, having a component thereof |
| US7198744B2 (en) * | 2002-08-06 | 2007-04-03 | The Goodyear Tire & Rubber Company | Preparation of co-extruded multi-layered rubber composite and use as component of a tire |
| US6959743B2 (en) * | 2002-09-13 | 2005-11-01 | The Goodyear Tire & Rubber Company | Tire with silica-rich tread cap layer and carbon black-rich supporting transition zone of intermediate and base layers |
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| JP4977304B2 (en) * | 2003-03-20 | 2012-07-18 | 株式会社ブリヂストン | Pneumatic tire |
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| US7891391B2 (en) * | 2006-09-08 | 2011-02-22 | The Goodyear Tire & Rubber Company | Tire with tread having an outer cap layer and underlying transition layer containing at least one of depolymerized rubber, pre-cured rubber and coal dust |
| US20090071584A1 (en) | 2007-09-19 | 2009-03-19 | Ping Zhang | Tire having tread with an internal closed cellular rubber transition layer |
| US20100018618A1 (en) * | 2008-07-24 | 2010-01-28 | Brandy Elizabeth Moorhead | Tire with tread having a two-ply tread cap layer |
| CN101440176A (en) * | 2008-12-24 | 2009-05-27 | 昊华南方(桂林)橡胶有限责任公司 | Giant engineering tire tread rubber and giant engineering tyre using the same |
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2010
- 2010-03-16 US US12/724,440 patent/US8439095B2/en not_active Expired - Fee Related
-
2011
- 2011-03-10 BR BRPI1101074-6A patent/BRPI1101074A2/en not_active IP Right Cessation
- 2011-03-10 EP EP11157756A patent/EP2366559B1/en not_active Not-in-force
- 2011-03-16 CN CN201110063034.1A patent/CN102189897B/en not_active Expired - Fee Related
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| US4739811A (en) * | 1982-10-20 | 1988-04-26 | Semperit Reifen Aktiengesellschaft | Pneumatic vehicle tire with radial ply carcass and tread member composed of a base layer situated closer to the tire axis and a cap layer arranged on top thereof |
| JP2668358B2 (en) * | 1987-04-22 | 1997-10-27 | 横浜ゴム株式会社 | Radial tire |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2366559B1 (en) | 2012-10-24 |
| CN102189897A (en) | 2011-09-21 |
| US8439095B2 (en) | 2013-05-14 |
| EP2366559A1 (en) | 2011-09-21 |
| BRPI1101074A2 (en) | 2012-08-21 |
| US20110226396A1 (en) | 2011-09-22 |
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